CN109181690B - Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe - Google Patents

Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe Download PDF

Info

Publication number
CN109181690B
CN109181690B CN201811298081.2A CN201811298081A CN109181690B CN 109181690 B CN109181690 B CN 109181690B CN 201811298081 A CN201811298081 A CN 201811298081A CN 109181690 B CN109181690 B CN 109181690B
Authority
CN
China
Prior art keywords
silver
nano grain
quantum dot
carbon quantum
cymoxanil
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811298081.2A
Other languages
Chinese (zh)
Other versions
CN109181690A (en
Inventor
桂日军
姜晓文
金辉
孙玉娇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Qingdao University
Original Assignee
Qingdao University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Qingdao University filed Critical Qingdao University
Priority to CN201811298081.2A priority Critical patent/CN109181690B/en
Publication of CN109181690A publication Critical patent/CN109181690A/en
Priority to US16/614,378 priority patent/US10900899B1/en
Priority to PCT/CN2019/078075 priority patent/WO2020087835A1/en
Application granted granted Critical
Publication of CN109181690B publication Critical patent/CN109181690B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/40—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having a double or triple bond to nitrogen, e.g. cyanates, cyanamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6432—Quenching
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6489—Photoluminescence of semiconductors

Abstract

The invention belongs to the preparation technical fields of nano material and fluorescence probe, and in particular to a kind of preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe.Prepare double transmitting carbon quantum dots and nano grain of silver, inner filtering effect occurs using between double transmitting carbon quantum dot and the nano grain of silver of dispersion, the blue-fluorescence of carbon quantum dot is caused to be quenched, and cymoxanil is specifically bound with nano grain of silver, nano grain of silver is caused to be assembled, inner filtering effect occurs between double transmitting carbon quantum dot and the nano grain of silver of dispersion, the green fluorescence of carbon quantum dot is caused to be quenched.Based on this, the linear relationship between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration is established, constructs the ratio fluorescent probe for cymoxanil detection.Probe preparation process is simple, and preparation cost is low, product high sensitivity, can develop into a kind of novel cymoxanil ratio fluorescent probe, the efficient detection for cymoxanil in pesticide.

Description

Based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe Preparation method
Technical field:
The invention belongs to the preparation technical fields of nano material and fluorescence probe, and in particular to one kind is based on double transmitting quantum The probe of the preparation method of point/nano grain of silver compound cymoxanil ratio fluorescent probe, preparation can be used for the height of cymoxanil Effect detection.
Background technique:
Cymoxanil is a kind of efficient, less toxic fungicide, is widely used in the vegetables such as cucumber, grape, tomato, lichee and fruit It is fresh-keeping and storage in.Cymoxanil is usually used with other pestsides synthesis, to reinforce the drug effect of pesticide.Human body is daily from vegetables water It is absorbed nourishment in fruit to meet somagenic need, the remains of pesticide in gourd, fruit and vegetable can cause damages to human health.A small amount of residual Pesticide human body itself can degrade, acute poisoning will not be caused, but long-term consumption does not clean up the agriculture with remains of pesticide Product can bring serious harm to human health.Cymoxanil is widely used in fruit and vegetables, easily detects it in pericarp Residual.Pesticide residue can be dispersed in water body by modes such as volatilization, runoff, leachings, and cymoxanil also has aquatile High toxicity can generate long-term adverse effect to water body environment.In the residual limit standard of European Union's agriculture, cymoxanil maximum is added Amount is 0.05 mg/kg, and human body Excess free enthalpy cymoxanil will lead to body immunity decline, aggravate burden of liver, lead to stomach Intestines problem results even in cancer in severe case.Unreasonable addition cymoxanil can cause a series of safety problem, Therefore, quantitative detection is carried out to cymoxanil to have great importance.
Anne-Claire etc. has detected cymoxanil (Pesticide residues in using three kinds of chromatographies raspberries and lettuce:Extrection and comparision of three chromatographic methods:HPLC,HPTLC and GC,Anne-Claire Martel,Maurice Porthault,J.LIQ.,CHROM.& REL.TECHNOL.,2000,23,3043–3058)；Matt J. etc. has detected cymoxanil using gas chromatography (Development of a Gas Chromatographic Method for Fungicide Cymoxanil Analysis in Dried Hops,Matt J.Hengel,Takayuki Shibamoto,J.Agric.Food Chem.,2001,49, 570–573)；Hulya Mercan etc. has detected cymoxanil content (Determination of in pesticide using stripping voltammetry Cymoxanil Fungicide in Commercial Formulation and Natural Water by Square- wave Stripping Voltammetry,Hulya Mercan,Recai.Inam,Clean-Soil,Air,Water 2010, 38,558–564).In the method for current detection cymoxanil, red, orange, green, blue, yellow (ROGBY) is mainly used, such as high liquid chromatography method (HPLC), Tablets by HPLC-MS (HPLC-MS) and gas chromatography (GC), other methods include ultrasound assisted extraction method, Microwave―assisted extraction, infra-red sepectrometry (FTIR) etc..Using existing when chromatography, detection limit is poor, and the spectral line of many samples can It can be overlapped, it can not specific recognition.There is also some defects, such as expensive equipment for other methods, and at high cost, sample pretreatment is multiple It is miscellaneous, high operation requirements etc..
Fluorescence analysis be position and its intensity of a kind of fluorescent line according to predetermined substance carry out identification and The instrument analytical method of assay.Many advantages, such as this method has high sensitivity, highly selective, easy to operate.In pesticide The advantages that context of detection, fluorescence analysis have sensitivity for analysis height, and selectivity is good, easy to operate.In current fluorescence detection In pesticide report, the main interaction for utilizing fluorescence quantum and pesticide causes quantum dot fluorescence Strength Changes to detect agriculture Medicine, this method depend on single fluorescence signal output mode.Single fluorescence signal detection method, vulnerable to background fluorescence, examination The influence of the factors such as agent, system and environmental condition, so as to cause the unstability of measurement result.In comparison, using dual signal Ratio proccessing obtains the volume efficiency of signal, can have self-calibration function, effectively eliminates self and background signal interference, mentions The high accuracy and reliability of testing result.Based on this, the present invention devises a kind of based on double emissive quantum dots/nano grain of silver The novel ratio fluorescent detecting probe method of compound, the efficient detection for cymoxanil.Up to now, there has been no use ratio fluorescent Detecting probe method detects cymoxanil, and detects frost based on double emissive quantum dots/nano grain of silver compound ratio fluorescent probe The domestic and foreign literature of urea cyanogen and the report of patent.
Summary of the invention:
It is an object of the invention to overcome the problems of the above-mentioned prior art, design a kind of method it is simple, it is low in cost, The preparation method based on double transmitting carbon quantum dot/nano grain of silver compound cymoxanil ratio fluorescent probes of high sensitivity.
To achieve the goals above, of the present invention a kind of based on double transmitting carbon quantum dot/nano grain of silver compounds The preparation process of cymoxanil ratio fluorescent probe the following steps are included:
1. a kind of preparation side based on double transmitting carbon quantum dot/nano grain of silver compound cymoxanil ratio fluorescent probes Method, which is characterized in that this method specifically includes the following steps:
(1) preparation of nano grain of silver: preparing 100 mM/ls of silver nitrate, 250 mM/ls of trisodium citrate and Prepared silver nitrate and trisodium citrate are added in 100 milliliters of secondary distilled waters by 5 mM/ls of sodium borohydride, Under magnetic agitation, 1 milliliter of sodium borohydride solution is added, obtains yellow solution after being stirred to react 30 minutes, this solution is centrifuged, second Alcohol washing and low-temperature vacuum drying processing, obtain nano grain of silver, the nano grain of silver of preparation is kept in dark place at 4 DEG C, for subsequent Experiment uses；
(2) preparation of carbon quantum dot: by 54.5 milligrams of 3- amino-phenols and 32.0 milligrams of oxalic acid be added to 50 milliliters it is secondary It in distilled water, is uniformly mixed, is then reacted under heating water bath under magnetic stirring, transparent homogeneous mixed solution is obtained, by this Solution is transferred in autoclave, heats 12 hours at 180 DEG C, after reaction, reaction mixture is cooled to room temperature, and is used 0.22 μm of membrane filtration removes large granular impurity, and filtrate alternately washes twice by revolving water removal, acetone and ethyl alcohol, then carries out cold Freeze and be dried, until moisture content all steams, the carbon quantum dot powder of preparation saves at room temperature, for further use；
(3) nano grain of silver made from step (1) is configured to aqueous solution, 10 points is reacted under room temperature and slow magnetic agitation Clock forms nano grain of silver homogeneous solution；
(4) carbon quantum dot made from step (2) is configured to aqueous solution, under room temperature and slow magnetic agitation, silver is added Nanoparticle solution configures the carbon quantum dot solution containing different nano grain of silver concentration, reacts 20 minutes and is formed under magnetic stirring Matter solution measures under different nano grain of silver concentration, the fluorescence emission spectrum of carbon quantum dot, is fitted two fluorescent emissions of carbon quantum dot Linear relationship between peak intensity ratio and nano grain of silver concentration；
(5) it is added cymoxanil into the carbon quantum dot aqueous solution containing nano grain of silver made from step (4), it is anti-under magnetic agitation 20 minutes formation homogeneous solutions are answered, are measured under different cymoxanil molar concentrations, the fluorescent emission of carbon quantum dot in homogeneous solution Spectrum, the linear relationship being fitted between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration, is constructed Ratio fluorescent probe for cymoxanil detection.
The present invention relates to the step of (1) described in nano grain of silver having a size of 5~20 nanometers, silver nitrate volumetric usage be 100~500 microlitres, trisodium citrate volumetric usage is 100~500 microlitres；Carbon quantum dot described in step (2) is having a size of 1 ~10 nanometers；Nano grain of silver mass concentration described in step (3) is 0.1~1.0 mcg/ml；Carbon described in step (4) The mass concentration that quantum dot is configured to aqueous solution is 0.1~1.0 mcg/ml, and nano grain of silver mass concentration is 0.01~0.2 micro- The mass concentration ratio of grams per milliliter, carbon quantum dot and nano grain of silver is 1:5~5:1；Step contains nano grain of silver described in (5) Carbon quantum dot solution and the mass concentration ratio of cymoxanil be 1:5~5:1, the linear detection range of cymoxanil molar concentration is 0.01~1.0 micromoles per liter, the detectable limit of cymoxanil molar concentration are 0.01~0.05 micromoles per liter.
Compared with prior art, the present invention using filter effect in occurring between double transmitting carbon quantum dots and the nano grain of silver of dispersion It answers, the blue-fluorescence of carbon quantum dot is caused to be quenched, and cymoxanil is specifically bound with nano grain of silver, causes nano grain of silver poly- Collection, occurs inner filtering effect between double transmitting carbon quantum dot and the nano grain of silver of dispersion, the green fluorescence of carbon quantum dot is caused to be quenched. Based on this, the linear relationship between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration, structure are established Build out the ratio fluorescent probe for cymoxanil detection；Its preparation process is simple, and preparation cost is low, product high sensitivity, can Develop into a kind of novel cymoxanil ratio fluorescent probe, the efficient detection for cymoxanil in pesticide.
Detailed description of the invention:
Fig. 1 is of the present invention a kind of glimmering based on double transmitting carbon quantum dot/nano grain of silver compound cymoxanil ratios The preparation of light probe and the schematic illustration of cymoxanil ratio fluorescent probe in detecting；
Fig. 2 is that cymoxanil ratio fluorescent probe of the present invention increases with cymoxanil molar concentration to double transmitting carbon quantums Linear pass between the response and fluorescence peak volume efficiency and cymoxanil molar concentration of two fluorescence emission peak strength signals of point System.
Specific embodiment:
The present invention is described in detail with reference to the accompanying drawing and by specific embodiment.
Embodiment 1:
It is of the present invention a kind of based on the spy of double transmitting carbon quantum dot/nano grain of silver compound cymoxanil ratio fluorescents The preparation and cymoxanil ratio fluorescent signal detection of needle, preparation process and schematic illustration are as shown in Figure 1, its concrete technology walks Suddenly are as follows:
The preparation of nano grain of silver: 100 mM/ls of silver nitrate, 250 mM/ls of trisodium citrate and 5 millis are prepared Prepared silver nitrate and trisodium citrate are added in 100 milliliters of secondary distilled waters, in magnetic by the sodium borohydride of mol/L Under power stirring, 1 milliliter of sodium borohydride solution is added, obtains yellow solution after being stirred to react 30 minutes, this solution is centrifuged, ethyl alcohol Washing and low-temperature vacuum drying processing, obtain nano grain of silver, the nano grain of silver of preparation is kept in dark place at 4 DEG C, for subsequent reality Test use.
The preparation of carbon quantum dot: 54.5 milligrams of 3- amino-phenols and 32.0 milligrams of oxalic acid are added to 50 milliliters of second distillations It in water, is uniformly mixed, is then reacted under heating water bath under magnetic stirring, obtain transparent homogeneous mixed solution, by this solution It is transferred in autoclave, heats 12 hours, after reaction, reaction mixture is cooled to room temperature, with 0.22 μm at 180 DEG C Membrane filtration removes large granular impurity, and filtrate alternately washes twice by revolving water removal, acetone and ethyl alcohol, then is freeze-dried Processing, until moisture content all steams, the carbon quantum dot powder of preparation saves at room temperature, for further use.
The nano grain of silver that average-size obtained is 5 nanometers is configured to aqueous solution, under room temperature and slow magnetic agitation Reaction 10 minutes forms nano grain of silver homogeneous solution, the carbon quantum dot that average-size obtained is 2 nanometers is configured to water-soluble Nano grain of silver solution is added under room temperature and slow magnetic agitation in liquid, and carbon quantum dot of the configuration containing different nano grain of silver concentration is molten Liquid reacts 20 minutes formation homogeneous solutions under magnetic stirring, measures under different nano grain of silver concentration, the fluorescence hair of carbon quantum dot Spectrum is penetrated, the linear relationship being fitted between two fluorescence emission peak volume efficiencies of carbon quantum dot and nano grain of silver concentration, wherein silver The mass concentration of nanoparticle and carbon quantum dot is respectively 0.1~0.5 mcg/ml and 0.01~0.1 mcg/ml.
Cymoxanil is added into the carbon quantum dot aqueous solution obtained containing nano grain of silver, reacts 20 minutes shapes under magnetic agitation It at homogeneous solution, measures under different cymoxanil molar concentrations, the fluorescence emission spectrum of carbon quantum dot in homogeneous solution, is fitted carbon Linear relationship between two fluorescence emission peak volume efficiencies of quantum dot and cymoxanil molar concentration is constructed and is examined for cymoxanil The ratio fluorescent probe of survey measures carbon quantum dot fluorescence emission spectrum under different cymoxanil molar concentrations, is fitted two fluorescence Emission peak intensity ratio I425/I525With cymoxanil concentration CCYMBetween linear relationship (referring to fig. 2) i.e. I425/I525=0.7180+ 1.7922CCYM(R2=0.9920), wherein cymoxanil concentration range is 0.05~0.50 micromoles per liter, cymoxanil detectable limit For 0.02 micromoles per liter.
Embodiment 2:
Nano grain of silver and the specific process step of carbon quantum dot preparation are with embodiment 1 in the present embodiment, wherein the nitre being added The volumetric usage of sour silver and trisodium citrate increased compared with embodiment 1, the silver nanoparticle for being 10 nanometers by average-size obtained Grain is configured to aqueous solution, reacts 10 minutes under room temperature and slow magnetic agitation, forms nano grain of silver homogeneous solution, will be obtained Average-size is that 5 nanometers of carbon quantum dot is configured to aqueous solution, and under room temperature and slow magnetic agitation, it is molten that nano grain of silver is added Liquid configures the carbon quantum dot solution containing different nano grain of silver concentration, reacts 20 minutes formation homogeneous solutions under magnetic stirring, surveys Under fixed different nano grain of silver concentration, the fluorescence emission spectrum of carbon quantum dot is fitted two fluorescent emission peak intensity ratios of carbon quantum dot Linear relationship between rate and nano grain of silver concentration, wherein the mass concentration of nano grain of silver and carbon quantum dot is respectively 0.2~ White urea is added into the carbon quantum dot aqueous solution obtained containing nano grain of silver for 0.8 mcg/ml and 0.02~0.2 mcg/ml Cyanogen reacts 20 minutes formation homogeneous solutions under magnetic agitation, measures under different cymoxanil molar concentrations, carbon amounts in homogeneous solution The fluorescence emission spectrum of son point, the line being fitted between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration Sexual intercourse constructs the ratio fluorescent probe for cymoxanil detection, measures carbon quantum dot under different cymoxanil molar concentrations Fluorescence emission spectrum is fitted two fluorescence emission peak volume efficiency I425/I525With cymoxanil concentration CCYMBetween linear relationship, Wherein cymoxanil concentration range is 0.02~0.5 micromoles per liter, and cymoxanil detectable limit is 0.01 micromoles per liter.
Embodiment 3:
Nano grain of silver and the specific process step of carbon quantum dot preparation are with embodiment 1 in the present embodiment, wherein the nitre being added The volumetric usage of sour silver and trisodium citrate increased compared with embodiment 1, the silver nanoparticle for being 15 nanometers by average-size obtained Grain is configured to aqueous solution, reacts 10 minutes under room temperature and slow magnetic agitation, forms nano grain of silver homogeneous solution, will be obtained Average-size is that 8 nanometers of carbon quantum dot is configured to aqueous solution, and under room temperature and slow magnetic agitation, it is molten that nano grain of silver is added Liquid configures the carbon quantum dot solution containing different nano grain of silver concentration, reacts 20 minutes formation homogeneous solutions under magnetic stirring, surveys Under fixed different nano grain of silver concentration, the fluorescence emission spectrum of carbon quantum dot is fitted two fluorescent emission peak intensity ratios of carbon quantum dot Linear relationship between rate and nano grain of silver concentration, wherein the mass concentration of nano grain of silver and carbon quantum dot is respectively 0.5~ White urea is added into the carbon quantum dot aqueous solution obtained containing nano grain of silver for 1.0 mcg/mls and 0.05~0.2 mcg/ml Cyanogen reacts 20 minutes formation homogeneous solutions under magnetic agitation, measures under different cymoxanil molar concentrations, carbon amounts in homogeneous solution The fluorescence emission spectrum of son point, the line being fitted between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration Sexual intercourse constructs the ratio fluorescent probe for cymoxanil detection, measures carbon quantum dot under different cymoxanil molar concentrations Fluorescence emission spectrum is fitted two fluorescence emission peak volume efficiency I425/I525With cymoxanil concentration CCYMBetween linear relationship, Wherein cymoxanil concentration range is 0.05~1.0 micromoles per liter, and cymoxanil detectable limit is 0.05 micromoles per liter.

Claims (6)

1. a kind of preparation method based on double transmitting carbon quantum dot/nano grain of silver compound cymoxanil ratio fluorescent probes, Be characterized in that, this method specifically includes the following steps:
(1) 100 mM/ls of silver nitrate, 250 mM/ls of trisodium citrate and 5 millis the preparation of nano grain of silver: are prepared Prepared silver nitrate and trisodium citrate are added in 100 milliliters of secondary distilled waters, in magnetic by the sodium borohydride of mol/L Under power stirring, 1 milliliter of sodium borohydride solution is added, obtains yellow solution after being stirred to react 30 minutes, this solution is centrifuged, ethyl alcohol Washing and low-temperature vacuum drying processing, obtain nano grain of silver, the nano grain of silver of preparation is kept in dark place at 4 DEG C, for subsequent reality Test use；
(2) 54.5 milligrams of 3- amino-phenols and 32.0 milligrams of oxalic acid the preparation of carbon quantum dot: are added to 50 milliliters of second distillations It in water, is uniformly mixed, is then reacted under heating water bath under magnetic stirring, obtain transparent homogeneous mixed solution, by this solution It is transferred in autoclave, heats 12 hours, after reaction, reaction mixture is cooled to room temperature, with 0.22 μm at 180 DEG C Membrane filtration removes large granular impurity, and filtrate alternately washes twice by revolving water removal, acetone and ethyl alcohol, then is freeze-dried Processing, until moisture content all steams, the carbon quantum dot powder of preparation saves at room temperature, for further use；
(3) nano grain of silver made from step (1) is configured to aqueous solution, is reacted 10 minutes under room temperature and slow magnetic agitation, Form nano grain of silver homogeneous solution；
(4) carbon quantum dot made from step (2) is configured to aqueous solution, under room temperature and slow magnetic agitation, silver nanoparticle is added Grain solution, configures the carbon quantum dot solution containing different nano grain of silver concentration, and it is molten to react 20 minutes formation homogeneous under magnetic stirring Liquid measures under different nano grain of silver concentration, the fluorescence emission spectrum of carbon quantum dot, is fitted two fluorescent emission peak intensities of carbon quantum dot Spend the linear relationship between ratio and nano grain of silver concentration；
(5) cymoxanil is added into the carbon quantum dot aqueous solution containing nano grain of silver made from step (4), reacts 20 under magnetic agitation Minute forms homogeneous solution, measures under different cymoxanil molar concentrations, the fluorescence emission spectrum of carbon quantum dot in homogeneous solution, The linear relationship being fitted between two fluorescence emission peak volume efficiencies of carbon quantum dot and cymoxanil molar concentration is constructed for frost The ratio fluorescent probe of urea cyanogen detection.
2. the method as described in claim 1, characterized in that the nano grain of silver in the step (1) having a size of 5~20 nanometers, Silver nitrate volumetric usage is 100~500 microlitres, and trisodium citrate volumetric usage is 100~500 microlitres.
3. the method as described in claim 1, characterized in that the carbon quantum dot in the step (2) is having a size of 1~10 nanometer.
4. the method as described in claim 1, characterized in that nano grain of silver mass concentration in the step (3) is 0.1~ 1.0 mcg/ml.
5. the method as described in claim 1, characterized in that the carbon quantum dot in the step (4) is configured to the matter of aqueous solution Amount concentration is 0.1~1.0 mcg/ml, and nano grain of silver mass concentration is 0.01~0.2 mcg/ml, carbon quantum dot and Yin Na The mass concentration ratio of the grain of rice is 1:5~5:1.
6. the method as described in claim 1, characterized in that the carbon quantum dot containing nano grain of silver in the step (5) is molten Liquid and the mass concentration ratio of cymoxanil are 1:5~5:1, and the linear detection range of cymoxanil molar concentration is 0.01~1.0 micro- to rub You/liter, the detectable limit of cymoxanil molar concentration is 0.01~0.05 micromoles per liter.
CN201811298081.2A 2018-11-02 2018-11-02 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe Active CN109181690B (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
CN201811298081.2A CN109181690B (en) 2018-11-02 2018-11-02 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe
US16/614,378 US10900899B1 (en) 2018-11-02 2019-03-14 Method for preparing ratiometric fluorescent probe for cymoxanil based on double-emission quantun dot-silver nanoparticle complex
PCT/CN2019/078075 WO2020087835A1 (en) 2018-11-02 2019-03-14 Method for preparing cymoxanil ratio fluorescence probe based on dual emission quantum dot/silver nanoparticle complex

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811298081.2A CN109181690B (en) 2018-11-02 2018-11-02 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe

Publications (2)

Publication Number Publication Date
CN109181690A CN109181690A (en) 2019-01-11
CN109181690B true CN109181690B (en) 2019-06-25

Family

ID=64941466

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811298081.2A Active CN109181690B (en) 2018-11-02 2018-11-02 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe

Country Status (3)

Country Link
US (1) US10900899B1 (en)
CN (1) CN109181690B (en)
WO (1) WO2020087835A1 (en)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109181690B (en) * 2018-11-02 2019-06-25 青岛大学 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe
CN109856101B (en) * 2019-03-27 2019-09-24 青岛大学 The preparation method of the nano hybrid of ratio fluorescent and ratio electrochemical sensing
CN110174389A (en) * 2019-06-24 2019-08-27 贵州大学 A kind of kanamycins detection method based on carbon dots fluorescence inner filtering effect
CN110530832B (en) * 2019-08-26 2022-09-27 河南师范大学 Method for selectively determining 2, 4-dinitrophenol in surface water sample based on fluorescence analysis
CN110835528B (en) * 2019-11-22 2022-05-10 南宁师范大学 Preparation of composite fluorescent nano probe and detection method of hydrogen peroxide by using composite fluorescent nano probe
CN111912890B (en) * 2020-06-24 2022-08-12 西安理工大学 Preparation method of carbon quantum dot/nano-silver modified foamed nickel electrode
CN111595832B (en) * 2020-07-02 2022-07-15 南宁师范大学 Method for detecting organophosphorus pesticide based on carbon dots and cadmium telluride quantum dots serving as fluorescent probes
CN113218920B (en) * 2021-02-04 2022-12-23 安徽师范大学 Fluorescent carbon based on chrysanthemum preparation method of nano-microsphere and para-Hg 2+ Detection of Subtopril
CN113358620B (en) * 2021-02-26 2022-08-12 电子科技大学 Fluorescence analysis method for detecting chlorophyll and carotenoid contents by using graphene quantum dots
CN113292989B (en) * 2021-06-04 2023-06-16 青岛大学 Preparation method of lactic acid fluorescence nanometer biological probe based on enzyme catalytic reaction of cobalt ion coordination type boron quantum dot
CN115505067A (en) * 2021-06-22 2022-12-23 北京化工大学 Selective targeting brain natriuretic peptide polymer and application thereof
CN113465769B (en) * 2021-07-06 2023-04-28 长春工业大学 Preparation method of double-emission nano fluorescent thermometer
CN113563877B (en) * 2021-07-20 2023-07-14 西安工业大学 Preparation method of N-doped orange fluorescent carbon dot and application of N-doped orange fluorescent carbon dot in Ag+ detection
CN114518358B (en) * 2022-02-16 2023-10-27 四川农业大学 Three-color sensing probe for detecting pesticide residues, preparation method thereof, application and visual intelligent monitoring device and method for deep learning
CN116904190B (en) * 2022-11-16 2024-04-12 山东宏济堂制药集团股份有限公司 Fluorescent probe capable of simultaneously detecting hexavalent chromium and ascorbic acid and preparation method and application thereof
CN115808409A (en) * 2022-11-17 2023-03-17 山东大学 Construction of ratiometric fluorescence biosensor based on nano platform and double-signal amplification and miRNA detection application
CN115746840B (en) * 2022-11-28 2024-02-02 陕西科技大学 Yellow carbon quantum dot petroleum ether fluorescent probe solution, preparation method and application

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892043A (en) * 2010-03-18 2010-11-24 华中师范大学 Method for preparing gold nano particles and application of particles in detection of cyhalothrin
CN103808705A (en) * 2014-03-11 2014-05-21 吉林大学 Method for detecting glyphosate by quantum dots and gold nano-particles
CN103901008A (en) * 2014-04-18 2014-07-02 吉林大学 Detection on melamine in hen eggs through inner filtration effect of fluorescence

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107748153B (en) * 2017-11-15 2020-11-03 华北电力大学 Penicillium amine probe with fluorescence-ultraviolet dual-signal mode and application thereof
CN109181690B (en) * 2018-11-02 2019-06-25 青岛大学 Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101892043A (en) * 2010-03-18 2010-11-24 华中师范大学 Method for preparing gold nano particles and application of particles in detection of cyhalothrin
CN103808705A (en) * 2014-03-11 2014-05-21 吉林大学 Method for detecting glyphosate by quantum dots and gold nano-particles
CN103901008A (en) * 2014-04-18 2014-07-02 吉林大学 Detection on melamine in hen eggs through inner filtration effect of fluorescence

Also Published As

Publication number Publication date
US20210025820A1 (en) 2021-01-28
CN109181690A (en) 2019-01-11
US10900899B1 (en) 2021-01-26
WO2020087835A1 (en) 2020-05-07

Similar Documents

Publication Publication Date Title
CN109181690B (en) Preparation method based on double emissive quantum dots/nano grain of silver compound cymoxanil ratio fluorescent probe
US10913892B1 (en) Method for preparing ratiometric fluorescent probe for melamine based on silver nanocluster complex
CN106970061B (en) Carbon dots/copper nano-cluster compound ratio fluorescent dopamine probe preparation method
Zeng et al. Determination of melamine by flow injection analysis based on chemiluminescence system
Bordonaba et al. Electrochemical behaviour of polyphenol rich fruit juices using disposable screen-printed carbon electrodes: Towards a rapid sensor for antioxidant capacity and individual antioxidants
CN104777156A (en) Method for detecting phytic acid based on carbon dot fluorescence off-on mode
Jia et al. Flow injection determination of metoclopramide based on KMnO4—HCHO chemiluminescence in a micellar medium
CN106483112B (en) A kind of method that fluorescence and colorimetric double mode continuously detect arginine and copper ion
CN108645826B (en) Novel method for rapidly detecting ascorbic acid
CN109827937A (en) A method of utilizing fluorescent quenching quantitative analysis alizarin red content
CN113249115B (en) Preparation of metal organic framework composite material and application of metal organic framework composite material as ratio type fluorescent probe in detection of hydrogen peroxide and Pi
CN112705195B (en) Functional material for degrading and determining tetracycline, preparation method and application
CN109781694A (en) The rapid detection method of metal ion in a kind of grape wine
CN105503768A (en) Preparation method of alpha-oxoglutarate fluorescent/ultraviolet molecular probe and application of alpha-oxoglutarate fluorescent/ultraviolet molecular probe to biological samples
Si et al. Novel methods for the rapid detection of trace tetracyclines based on the fluorescence behaviours of Maillard reaction fluorescent nanoparticles
CN109053711B (en) Probe compound for mercury ion detection and preparation method and application thereof
CN103091305A (en) Method for detecting quinolone antibiotic by means of electrochemical luminescence
CN110408397A (en) A kind of CeCl3:Eu3+The preparation method of fluorescence probe array
CN109975268A (en) A method of nitrite ion is detected based on gold and silver core shell nanoparticles SERS technology
CN106872427B (en) H in a kind of carbon quantum dot targeting detection lysosome2The method of S
CN108645838A (en) A kind of method of dimehypo and Simanex field quick detection in tealeaves
CN110698390B (en) Fluorescent probe for identifying bisulfite and preparation method and detection method thereof
CN109632732B (en) Near-infrared fluorescence sensitization method for determining glucose
CN113861962A (en) Ratiometric fluorescent probe, preparation method thereof and application thereof in detection of hydrogen peroxide
CN110208232A (en) The method for quickly measuring ascorbic acid with nano cupric oxide self-activation cascade catalytic fluorometry system

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant